The present invention relates to a catalyst for olefin polymerization, a method for producing the catalyst, and a method for producing olefinic polymers. Precisely, it relates to a novel, high-activity metallocene catalyst for olefin polymerization, which has the advantage of high polymerization activity in vapor-phase or slurry polymerization to give olefinic polymers, to a method for producing the catalyst, and to a method of using the catalyst in producing olefinic polymers.
Heretofore used are Ziegler-Natta catalysts in producing polyolefins. In vapor-phase or slurry polymerization to give substantially granular polymer particles, polyolefins produced could have good morphology since the catalyst used is carried on a carrier such as magnesium chloride or silica gel. Recently, a method of using catalysts that comprise a metallocene compound and an aluminoxane has been proposed for producing polyolefins (Japanese Patent Laid-Open Nos. 019309/1983, 167307/1990, etc.). Being different from conventional Ziegler-Natta catalysts, such metallocene catalysts have enabled polymerization of giving polyolefins uniformly dissolved in solvents such as hydrocarbons, etc., and it is known that their polymerization activity per the transition metal therein is extremely high and they give polymers having a narrow molecular weight distribution. Applying metallocene catalysts that are characterized by such features to ordinary vapor-phase or slurry polymerization, if possible, is preferred, as they will not require any additional investment in plant and equipment. However, metallocene catalysts, if applied to vapor-phase or slurry polymerization, must be carried on carriers. One method of carrying metallocene catalysts on carriers is known, which comprises reacting methylaluminoxane with silica gel followed by carrying a metallocene catalyst on the resulting reaction product (Japanese Patent Laid-Open Nos. 188712/1997, 70227/1995, etc.). However, the method is problematic in that the polymerization activity of the metallocene catalyst carried on such a carrier and used therein is lower than that of a metallocene catalyst in a uniform polymerization system. One example of producing propylene in the presence of a prepolymerized solid catalyst, which is prepared by ultrasonically prepolymerizing an olefin with a catalyst, is disclosed in Japanese Patent Laid-Open No. 120716/1998. However, the prepolymerized solid catalyst is problematic in that it is unstable. At present, metallocene catalysts carried on carriers, which are substantially applicable to vapor-phase or slurry polymerization with no reduction in their activity, could not be obtained. In addition, even in uniform polymerization in which are usedmetallocene catalysts, a large amount of aluminoxanes relative to transition metals must be used. In this, therefore, there are the problems that the polymerization activity per aluminium of the catalysts used is low and that aluminium remains in the polymers produced.
From the viewpoints noted above, we, the inventors have made the present invention, and the object of the invention is to provide a novel high-activity metallocene catalyst for olefin polymerization, of which the activity is high even in vapor-phase or slurry polymerization to give olefinic polymers and which realizes reducing the amount of aluminoxanes to be used along with it, to provide a method for producing the catalyst, and to provide a method for producing olefinic polymers.
We, the present inventors have assiduously studied so as to attain the object as above, and, as a result, have found that a metallocene catalyst for olefin polymerization, which is obtained by subjecting a transition metal compound, an organoaluminiumoxy compound and optionally a carrier to specific treatment, more precisely, a metallocene catalyst for olefin polymerization, which is obtained by contacting a compound of a transition metal compound of Groups 4 to 6 of the Periodic Table, an organoaluminiumoxy compound and optionally a carrier with each other while being exposed to elastic waves, can effectively attain the object. On the basis of this finding, we have completed the present invention. Specifically, the invention provides a catalyst for olefin polymerization, a method for producing it, and a method for producing olefinic polymers, which are as follows:
1. A catalyst for olefin polymerization, which is obtained by contacting (A) a compound of a transition metal of Groups 4 to 6 of the Periodic Table, (B) an organoaluminiumoxy compound, and optionally (C) a carrier with each other, and for which they are exposed to elastic waves at least in any step of contacting them with each other.
2. The catalyst for olefin polymerization of above 1, in which (A) is any of the following general formula (I), (II) or (III):
Q1a(C5H5-a-bR1b)(C5H5-a-cR2c)M1X1pY1qxe2x80x83xe2x80x83(I)
Q2a(C5H5-a-dR3d)Z1M1X1pY1qxe2x80x83xe2x80x83(II)
(C5H5-a-dR3d)M1X1rY1sxe2x80x83xe2x80x83(III)
wherein Q1 represents a bonding group that crosslinks the two conjugated five-membered cyclic ligands (C5H5-a-bR1b) and (C5H5-a-cR2c); Q2 represents a bonding group that crosslinks the conjugated five-membered cyclic ligand (C5H5-a-dR3d) and the group Z1; R1, R2 and R3 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group; a represents 0, 1 or 2; b, c and d each represent an integer of from 0 to 5 when a=0, or an integer of from 0 to 4 when a=1, or an integer of from 0 to 3 when a=2; p+q=[(the valency of M1)xe2x88x922]; r+s=[(the valency of M1)xe2x88x921]; M1 represents a transition metal of Groups 4 to 6 of the Periodic Table; X1, Y1 and Z1 each represent a covalent-bonding or ionic-bonding ligand; plural X1xe2x80x2s and Y1xe2x80x2s, if any, may be the same or different, and may be bonded to each other to form a cyclic structure.
3. The catalyst for olefin polymerization of above 1 or 2, in which (C) has a mean particle size of from 1 to 300 xcexcm, a specific surface area of from 1 to 1000 m2/g, and a pore volume of from 0.1 to 5 cm3/g.
4. The catalyst for olefin polymerization of any of above 1 to 3, for which the elastic waves are ultrasonic waves.
5. The catalyst for olefin polymerization of any of above 1 to 4, for which the frequency of the ultrasonic waves falls between 1 and 1000 kHz.
6. A method for producing a catalyst for olefin polymerization, which comprises contacting (A) a compound of a transition metal of Groups 4 to 6 of the Periodic Table, (B) an organoaluminiumoxy compound, and optionally (C) a carrier with each other, and in which they are exposed to elastic waves at least in any step of contacting them with each other.
7. A method for producing olefinic polymers, which comprises polymerizing or copolymerizing olefins in the presence of the olefin polymerization catalyst of any of above 1 to 5.
8. A method for producing olefinic polymers, which comprises polymerizing or copolymerizing olefins in the presence of the olefin polymerization catalyst of any of above 1 to 5 and an organoaluminium compound.
The invention is a catalyst for olefin polymerization, which is obtained by contacting (A) a compound of a transition metal of Groups 4 to 6 of the Periodic Table, (B) an organoaluminiumoxy compound, and optionally (C) a carrier with each other, and for which they are exposed to elastic waves at least in any step of contacting them with each other; a method for producing the catalyst; and a method of using the catalyst for producing olefinic polymers. The olefin polymerization catalyst [I]; the method for producing the catalyst [II]; and the method for producing olefinic polymers [III] are described in detail hereinunder.
The olefin polymerization catalyst of the invention is obtained by contacting (A) a compound of a transition metal of Groups 4 to 6 of the Periodic Table, (B) an organoaluminiumoxy compound, and optionally (C) a carrier with each other, for which they are exposed to elastic waves at least in any step of contacting them with each other.
(A) Compound of Transition Metal of Groups 4 to 6 of the Periodic Table:
The compound of a transition metal of Groups 4 to 6 of the Periodic Table (A) includes metallocenes. Metallocenes include transition metal compounds having one or two ligands of a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group and the like, and also transition metal compounds having the ligands geometrically controlled, such as those described in Japanese Patent Laid-Open Nos. 19309/1983, 130314/1986, 163088/1991, 300887/1992 and 211694/1992, International Patent Publication No. 502036/1989, etc., and they are characterized by uniform properties of the active points therein. Above all for the component (A) in the invention, preferred are metallocenes of the following general formula (I), (II) or (III):
Q1a(C5H5-a-bR1b)(C5H5-a-cR2c)M1X1pY1qxe2x80x83xe2x80x83(I)
Q2a(C5H5-a-dR3d)Z1M1X1pY1qxe2x80x83xe2x80x83(II)
(C5H5-a-dR3d)M1X1rY1sxe2x80x83xe2x80x83(III)
wherein Q1 represents a bonding group that crosslinks the two conjugated five-membered cyclic ligands (C5H5-a-bR1b) and (C5H5-a-cR2c); Q2 represents a bonding group that crosslinks the conjugated five-membered cyclic ligand (C5H5-a-dR3d) and the group Z1; R1, R2 and R3 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group; a represents 0, 1 or 2; b, c and d each represent an integer of from 0 to 5 when a=0, or an integer of from 0 to 4 when a=1, or an integer of from 0 to 3 when a=2; p+q=[(the valency of M1)xe2x88x922]; r+s=[(the valency of M1)xe2x88x921]; M1 represents a transition metal of Groups 4 to 6 of the Periodic Table; X1, Y1 and Z1 each represent a covalent-bonding or ionic-bonding ligand; plural X1xe2x80x2s and Y1xe2x80x2s, if any, may be the same or different, and may be bonded to each other to form a cyclic structure.
Specific examples of Q1 and Q2 include (1) an alkylene group having from 1 to 4 carbon atoms, or a cycloalkylene group, or the group substituted by a lower alkyl or phenyl group at its side chain, such as a methylene group, an ethylene group, an isopropylene group, a methylphenylmethylene group, a diphenylmethylene group, a cyclohexylene group, etc.; (2) a silylene group, or an oligosilylene group, or the group substituted by a lower alkyl or phenyl group at its side chain, such as a silylene group, a dimethylsilylene group, a methylphenylsilylene group, a diphenylsilylene group, a disilylene group, a tetramethyldisilylene group, etc.; and (3) a hydrocarbon group (e.g., a lower alkyl group, a phenyl group, a hydrocarbyloxy group (preferably, a lower alkoxy group), etc.) containing germanium, phosphorus, nitrogen, boron or aluminium, such as a (CH3)2Ge group, a (C6H5)2Ge group, a (CH3)2P group, a (C6H5)2P group, a (C4H9)N group, a (C6H5)N group, a (CH3)B group, a (C4H9)B group, a (C6H5)B group, a (C6H5)Al group, a (CH3O)Al group, etc. Of those, preferred are alkylene groups and silylene groups in view of their activity.
(C5H5-a-bR1b), (C5H5-a-cR2c) and (C5H5-a-dR3d) are conjugated, 5-membered cyclic ligands, in which R1, R2 and R3 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group; a represents 0, 1 or 2; and b, c and d each represent an integer of from 0 to 5 when a=0, or an integer of from 0 to 4 when a=1, or a integer of from 0 to 3 when a=2. The hydrocarbon group preferably has from 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms. The hydrocarbon group may be a monovalent one that bonds to the cyclopentadienyl group of a conjugated, 5-membered cyclic group. Two of plural hydrocarbon groups, if any, may be bonded to each other to form a cyclic structure along with a part of the cyclopentadienyl group. Specific examples of those conjugated, 5-membered cyclic ligands are substituted or unsubstituted cyclopentadienyl groups, indenyl groups and fluorenyl groups. The halogen atom includes chlorine, bromine, iodine and fluorine atoms. The alkoxy group preferably has from 1 to 12 carbon atoms. The silicon-containing hydrocarbon group includes, for example, groups of xe2x88x92Si(R4) (R5) (R6), in which R4, R5 and R6 each represent a hydrocarbon group having from 1 to 24 carbon atoms. As the phosphorus-containing hydrocarbon group, the nitrogen-containing hydrocarbon group and the boron-containing hydrocarbon group, for example, mentioned are groups of xe2x80x94P(R7) (R8), xe2x80x94N(R7) (R8), and xe2x80x94B(R7) (R8), respectively, in which R7 and R8 each represent a hydrocarbon group having from 1 to 18 carbon atoms. Plural R1xe2x80x2s, R2xe2x80x2s and R3xe2x80x2s, if any, may be the same or different ones, respectively. In formula (I), the conjugated, 5-membered cyclic ligands (C5H5-a-bR1b) and (C5H5-a-cR2c) may be the same or different ones.
M1 represents a transition metal element of Groups 4 to 6 of the Periodic Table, including, for example, titanium, zirconium, hafnium, vanadium, niobium, molybdenum, tungsten, etc. Of those, preferred are titanium, zirconium and hafnium in view of their activity. Z1 represents a covalent-bonding ligand, including, for example, a halogen atom, an oxygen atom (xe2x80x94Oxe2x80x94), a sulfur atom (xe2x80x94Sxe2x80x94), an alkoxy group having from 1 to 20, preferably from 1 to 10 carbon atoms, a thioalkoxy group having from 1 to 20, preferably from 1 to 12 carbon atoms, a nitrogen-containing hydrocarbon group having from 1 to 40, preferably from 1 to 18 carbon atoms, and a phosphorus-containing hydrocarbon group having from 1 to 40, preferably from 1 to 18 carbon atoms. X1 and Y1 may be bonded to each other to form a cyclic structure. Specifically, plural X1xe2x80x2s, if any, may be bonded to each other to form a cyclic structure; or plural Y1xe2x80x2s, if any, may be bonded to each other to form a cyclic structure; or X1 and Y1 may be bonded to each other to form a cyclic structure. X1 and Y1 each represent a covalent-bonding or ionic-bonding ligand, including, for example, a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20, preferably from 1 to 10 carbon atoms, an alkoxy group having from 1 to 20, preferably from 1 to 10 carbon atoms, an amino group, a phosphorus-containing hydrocarbon group having from 1 to 20, preferably from 1 to 12 carbon atoms (e.g., a diphenylphosphine group, etc.) a silicon-containing hydrocarbon group having from 1 to 20, preferably from 1 to 12 carbon atoms (e.g., a trimethylsilyl group, etc.), and a boron compound residue having a hydrocarbon group with from 1 to 20, preferably from 1 to 12 carbon atoms or having halogens (e.g., B(C6H5)4, BF4). Of those, preferred are halogen atoms and hydrocarbon groups. X1 and Y1 may be the same or different ones.
Preferred and typical examples of the transition metal compounds of formula (I), (II) or (III) are those in which Q1 represents a bonding group that crosslinks the two conjugated five-membered cyclic ligands (C5H5-a-bR1b) and (C5H5-a-cR2c); Q2 represents a bonding group that crosslinks the conjugated five-membered cyclic ligand (C5H5-a-dR3d) and the group Z1; Q1 and Q2 each are an alkylene group or a silylene group; R1, R2 and R3 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group; a represents 0, 1 or 2; b, c and d each represent an integer of from 0 to 5 when a=0, or an integer of from 0 to 4 when a=1, or an integer of from 0 to 3 when a=2; p+q=[(the valency of M1)xe2x88x922]; r+s=[(the valency of M1)xe2x88x921]; M1 represents a transition metal of Groups 4 to 6 of the Periodic Table, and is titanium, zirconium or hafnium; X1, Y1 and Z1 each represent a covalent-bonding or ionic-bonding ligand and may be bonded to each other to form a cyclic structure; X1 and Y1 each are a halogen atom or a hydrocarbon group; Z1 is an alkoxy group having from 1 to 10 carbon atoms, a thioalkoxy group having from 1 to 12 carbon atoms, a nitrogen-containing hydrocarbon group having from 1 to 18 carbon atoms, or a phosphorus-containing hydrocarbon group having from 1 to 18 carbon atoms.
As specific examples of the transition metal compounds of formula (I) or (II), mentioned are the following compounds.
 less than 1 greater than  Transition metal compounds not having a crosslinkable bonding group but having two conjugated, 5-membered cyclic ligands, such as bis(cyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium dichloride, bis(dimethylcyclopentadienyl)zirconium dichloride, bis(trimethylcyclopentadienyl)zirconium dichloride, bis(tetramethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(fluorenyl)zirconium dichloride, bis(cyclopentadienyl)zirconium chlorohydride, bis(cyclopentadienyl)methylzirconium chloride, bis(cyclopentadienyl)methylzirconium chloride, bis(cyclopentadienyl)phenylzirconium chloride, bis(cyclopentadienyl)dimethylzirconium, bis(cyclopentadienyl)diphenylzirconium, bis(cyclopentadienyl)dineopentylzirconium, bis(cyclopentadienyl)dihydrozirconium, (cyclopentadienyl)(indenyl)zirconium dichloride, (cyclopentadienyl)(fluorenyl)zirconium dichloride, etc.
 less than 2 greater than  Transition metal compounds having two conjugated, 5-membered cyclic ligands, in which the two ligands are crosslinked with an alkylene group, such as
methylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, methylenebis(indenyl)zirconium chlorohydride, ethylenebis(indenyl)methylzirconium chloride, ethylenebis(indenyl)methoxychlorozirconium, ethylenebis(indenyl)zirconium diethoxide, ethylenebis(indenyl)dimethylzirconium, ethylenebis (4,5,6,7-tetrahydroindenyl)zirconium dichloride, ethylenebis(2-methylindenyl)zirconium dichloride, ethylenebis(2,4-dimethylindenyl)zirconium dichloride, ethylenebis (2-methyl-4-phenylindenyl)zirconium dichoride, ethylenebis(2-methyl-4-naphthylindenyl)zirconium dichloride, ethylenebis(2-methyl-4,5-benzoindenyl)zirconium dichloride, ethylenebis(2-methyl-4-trimethylsilylindenyl)zirconium dichloride, ethylenebis(2,4-dimethyl-5,6,7-trihydroindenyl)zirconium dichloride, ethylene(2,4-dimethylcyclopentadienyl)(3xe2x80x2,5xe2x80x2-dimethylcyclopentadienyl)zirconium dichloride, ethylene(2-methyl-4-t-butylcyclopentadienyl)(3xe2x80x2-t-butyl-5xe2x80x2-methylcyclopentadienyl)zirconium dichloride, ethylene(2,3,5-trimethylcyclopentadienyl)(2xe2x80x2,4xe2x80x2,5xe2x80x2-trimethylcyclopentadienyl)zirconium dichloride, isopropylidenebis(2-methylindenyl)zirconium dichloride, isopropylidenebis(indenyl)zirconium dichloride, isopropylidenebis (2,4-dimethylindenyl)zirconium dichloride, isopropylidene(2,4-dimethylcyclopentadienyl)(3xe2x80x2,5xe2x80x2-dimethylcyclopentadienyl)zirconium dichloride, isopropylidene(2-methyl-4-t-butylcyclopentadienyl)(3xe2x80x2-t-butyl-5xe2x80x2-methylcyclopentadienyl)zirconium dichloride, methylene(cyclopentadienyl)(3,4-dimethylcyclopentadienyl)zirconium dichloride, methylene(cyclopentadienyl)(3,4-dimethylcyclopentadienyl)zirconium chlorohydride, methylene(cyclopentadienyl)(3,4-dimethylcyclopentadienyl)dimethylzirconium, methylene(cyclopentadienyl)(3,4-dimethylcyclopentadienyl)diphenylzirconium, methylene(cyclopentadienyl)(trimethylcyclopentadienyl)-zirconium dichloride, methylene(cyclopentadienyl)(tetramethylcyclopentadienyl)-zirconium dichloride, isopropylidene(cyclopentadienyl)(3,4-dimethylcyclopentadienyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(3-methylindenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, isopropylidene(2-methylcyclopentadienyl)(fluorenyl)zirconium dichloride, isopropylidene(2,5-dimethylcyclopentadienyl)(3,4-dimethylcyclopentadienyl)zirconium dichloride, isopropylidene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride, ethylene(cyclopentadienyl)(3,5-dimethylcyclopentadienyl)zirconium dichloride, ethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, ethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride, ethylene(2,5-diethylcyclopentadienyl)(fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(3,4-diethylcyclopentadienyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(3,4-diethylcyclopentadienyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, cyclohexylidene(2,5-dimethylcyclopentadienyl)(3xe2x80x2,4xe2x80x2-dimethylcyclopentadienyl)zirconium dichloride, ethylenebis(2,4,7-trimethylindenyl)zirconium dichloride, etc.
 less than 3 greater than  Transition metal compounds having two silylene-crosslinked, conjugated, 5-membered cyclic ligands, such as dimethylsilylenebis(2,2,7-trimethylindenyl)zirconium dichloride, dimethylsilylenebis(indenyl)zirconium dichloride, dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, dimethylsilylenebis(2-methylindenyl)zirconium dichloride, dimethylsilylenebis(2,4-dimethylindenyl)zirconium dichloride, dimethylsilylenebis(2,4-dimethylcyclopentadienyl)(3xe2x80x2,5xe2x80x2-dimethylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(2-methyl-4,5-benzoindenyl)zirconium dichloride, dimethylsilylenebis(2-methyl-4-naphthylindenyl)zirconium dichloride, dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride, phenylmethylsilylenebis(indenyl)zirconium dichloride, phenylmethylsilylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, phenylmethylsilylenebis(2,4-dimethylindenyl)zirconium dichloride, phenylmethylsilylene(2,4-dimethylcyclopentadienyl)(3xe2x80x2,5xe2x80x2-dimethylcyclopentadienyl)zirconium dichloride, phenylmethylsilylene(2,3,5-trimethylcyclopentadienyl)(2xe2x80x2,4xe2x80x2,5xe2x80x2-trimethylcyclopentadienyl)zirconium dichloride, phenylmethylsilylenebis(tetramethylcyclopentadienyl)-zirconium dichloride, diphenylsilylenebis(2,4-dimethylindenyl)zirconium dichloride, diphenylsilylenebis(indenyl)zirconium dichloride, diphenylsilylenebis(2-methylindenyl)zirconium dichloride, tetramethyldisilylenebis(indenyl)zirconium dichloride, tetramethyldisilylenebis(cyclopentadienyl)zirconium dichloride, tetramethyldisilylene(3-methylcyclopentadienyl)(indenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(3,4-dimethylcyclopentadienyl)zirconium dichloride, dimethylsilylene-(cyclopentadienyl)(trimethylcyclopentadienyl)zirconium dichloride, dimethylsilylene-(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(3,4-diethylcyclopentadieny)zirconium dichloride, dimethylsilylene-(cyclopentadienyl)(triethylcyclopentadienyl)zirconium dichloride, dimethylsilylene-(cyclopentadienyl)(tetraethylcyclopentadienyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, dimethylsilylene-(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, dimethylsilylene(2-methylcyclopentadienyl)(fluorenyl)zirconium dichloride, dimethylsilylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride, dimethylsilylene(2-ethylcyclopenadienyl)(fluorenyl) zirconium dichloride, dimethylsilylene (2,5-diethylcyclopentadienyl)(fluorenyl)zirconium dichloride, diethylsilylene(2-methylcyclopentadienyl)(2xe2x80x2,7xe2x80x2-di-t-butylfluorenyl)zirconium dichloride, dimethylsilylene(2,5-dimethylcyclopentadienyl)(2xe2x80x2,7xe2x80x2-di-t-butylfluorenyl)zirconium dichloride, dimethylsilylene(2-ethylcyclopentadienyl)(2xe2x80x2,7xe2x80x2-di-t-butylfluorenyl)zirconium dichloride, dimethylsilylene(diethylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, dimethylsilylene-(methylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, dimethylsilylene-(dimethylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, dimethylsilylene-(ethylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, dimethylsilylene-(diethylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, etc.
 less than 4 greater than  Transition metal compounds having two conjugated, 5-membered cyclic ligands, in which the two ligands are crosslinked with a germanium-, aluminium-, boron-, phosphorus- or nitrogen-containing hydrocarbon group, such as dimethylgermylenebis(indenyl)zirconium dichloride, dimethylgermylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, methylalumylenebis(indenyl)zirconium dichloride, phenylaminylenebis(indenyl)zirconium dichloride, phenylphosphylenebis(indenyl)zirconium dichloride, ethylborylenebis(indenyl)zirconium dichloride, phenylaminylenebis(indenyl)zirconium dichloride, phenylaminylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, etc.
 less than 5 greater than  Transition metal compounds having one conjugated, 5-membered cyclic ligand, such as pentamethylcyclopentadienyl-bis(phenyl)aminozirconium dichloride, indenyl-bis(phenyl)aminozirconium dichloride, pentamethylcyclopentadienyl-bis(trimethylsilyl)aminozirconium dichloride, pentamethylcyclopentadienylphenoxyzirconium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)-t-butylaminozirconium dichloride, dimethylsilylene-(tetramethylcyclopentadienyl)phenylaminozirconium dichloride, dimethylsilylene(tetrahydroindenyl)decylaminozirconium dichloride, dimethylsilylene(tetrahydroindenyl)-[bis(trimethylsilyl)amino]zirconium dichloride, dimethylgermylene-(tetramethylcyclopentadienyl)phenylaminozirconium dichloride, pentamethylcyclopentadienylzirconium trimethoxide, pentamethylcyclopentadienylzirconium trichloride, (t-butylamido)(tetramethyl-xcex75-cyclopentadienyl)silane-titaniumdimethyl, (t-butylamido)(tetramethyl-xcex75-cyclopentadienyl)-1,2-ethane-diyltitanium dichloride, (methylamido)(tetramethyl-xcex75-cyclopentadienyl)-1,2-ethane-diyltitanium dichloride, (ethylamido)(tetramethyl-xcex75-cyclopentadienyl)-methylenetitanium dichloride, (t-butylamido)dimethyl-(tetramethyl-xcex75-cyclopentadienyl)silane-titaniumdichloride, (benzylamido)dimethyl-(tetramethyl-xcex75-cyclopentadienyl)silane-titanium dichloride, (phenylphosphido)dimethyl-(tetramethyl-xcex75-cyclopentadienyl)silane-titaniumdibenzyl, etc.
 less than 6 greater than  Transition metal compounds having two conjugated, 5-membered cyclic ligands in which the ligands are double-crosslinked, such as (1,1xe2x80x2-dimethylsilylene)(2,2xe2x80x2-isopropylene)bis(cyclopentadienyl)zirconium dichloride, (1,1xe2x80x2-dimethylsilylene)(2,2xe2x80x2-dimethylsilylene)bis(cyclopentadienyl) zirconium dichloride, (1,1xe2x80x2-dimethylsilylene)(2,2xe2x80x2-isopropylidene)-bis(cyclopentadienyl)dimethylzirconium, (1,1xe2x80x2-dimethylsilylene)(2,2xe2x80x2-isopropylidene)-bis(cyclopentadienyl)dibenzylzirconium, (1,1xe2x80x2-dimethylsilylene)(2,2xe2x80x2-isopropylidene)-bis(cyclopentadienyl)bis(trimethylsilyl)zirconium, (1,1xe2x80x2-dimethylsilylene)(2,2xe2x80x2-isopropylidene)-bis(cyclopentadienyl)bis(trimethylsilylmethyl)zirconium, (1,2xe2x80x2-dimethylsilylene)(2,1xe2x80x2-ethylene)-bis(indenyl)zirconium dichloride, (1,1xe2x80x2-dimethylsilylene)(2,2xe2x80x2-ethylene)-bis(indenyl)zirconium dichloride, (1,1xe2x80x2-ethylene)(2,2xe2x80x2-dimethylsilylene)-bis(indenyl)zirconium dichloride, (1,1xe2x80x2-dimethylsilylene)(2,2xe2x80x2-cyclohexylidene)-bis(indenyl)zirconium dichloride, (1,2xe2x80x2-dimethylsilylene)(2,1xe2x80x2-dimethylsilylene)bis(indenyl)zirconium dichloride, (1,2xe2x80x2-dimethylsilylene)(2,1xe2x80x2-dimethylsilylene)bis(3-methylindenyl)zirconium dichloride, (1,2xe2x80x2-dimethylsilylene)(2,1xe2x80x2-dimethylsilylene)bis(3-n-butylindenyl)zirconium dichloride, etc.
 less than 7 greater than  Derivatives from compounds of  less than 1 greater than  to  less than 6 greater than  noted above, which are produced by substituting the chlorine atoms in those compounds of  less than 1 greater than  to  less than 6 greater than  with any of a bromine atom, an iodine atom, a hydrogen atom, a methyl group, a phenyl group, a benzyl group, a methoxy group, a dimethylamino group and others, and/or by substituting the zirconium atom in those compounds with any of titanium, hafnium and other atoms.
As specific examples of the transition metal compounds of formula (III), mentioned are the following compounds.
Especially preferred are the transitionmetal compounds of formula (III) in which the group (C5H5-a-dR3d) is any of the following formulae (IV) to (X): 
wherein A represents an element of Group 13, 14, 15 or 16, and plural A""s maybe the same or different; R represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, a carboxyl group, or an alkylsilyl or alkylsilylalkyl group having from 3 to 30 carbon atoms, and R""s may be the same or different, and may be optionally bonded to each other to form a cyclic structure; a represents 0, 1 or 2; and n and m each represent an integer of at least 1.
Specific examples of the group (C5H5-a-dR3d) are mentioned below.
In the indenyl derivatives and the fluorenyl derivatives, the position of each substituent is indicated by the following position numbers. 
The group (C5H5-a-dR3d) includes, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, a 1,2-dimethylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group, a 1,2,3-trimethylcyclopentadienyl group, a 1,3,4-trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, an ethylcyclopentadienyl group, a 1,2-diethylcyclopentadienyl group, a 1,3-diethylcyclopentadienyl group, a 1,2,3-triethylcyclopentadienyl group, a 1,3,4-triethylcyclopentadienyl group, a tetraethylcyclopentadienyl group, a pentaethylcyclopentadienyl group, an indenyl group, a 1-methylindenyl group, a 1,2-dimethylindenyl group, a 1,3-dimethylindenyl group, a 1,2,3-trimethylindenyl group, a 2-methylindenyl group, a 1-ethylindenyl group, a 1-ethyl-2-methylindenyl group, a 1-ethyl-3-methylindenyl group, a 1-ethyl-2,3-dimethylindenyl group, a 1,2-diethylindenyl group, a 1,3-diethylindenyl group, a 1,2,3-triethylindenyl group, a 2-ethylindenyl group, a 1-methyl-2-ethylindenyl group, a 1,3-dimethyl-2-ethylindenyl group, a 4,5,6,7-tetrahydroindenyl group, a 1-methyl-4,5,6,7-tetrahydroindenyl group, a 1,2-dimethyl-4,5,6,7-tetrahydroindenyl group, a 1,3-dimethyl-4,5,6,7-tetrahydroindenyl group, a 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyl group, a 2-methyl-4,5,6,7-tetrahydroindenyl group, a 1-ethyl-4,5,6,7-tetrahydroindenyl group, a 1-ethyl-2-methyl-4,5,6,7-tetrahydroindenyl group, a 1-ethyl-3-methyl-4,5,6,7-tetrahydroindenyl group, a 1-ethyl-2,3-dimethyl-4,5,6,7-tetrahydroindenyl group, a 1,2-diethyl-4,5,6,7-tetrahydroindenyl group, a 1,2-diethyl-3-methyl-4,5,6,7-tetrahydroindenyl group, a 1,3-diethyl-4,5,6,7-tetrahydroindenyl group, a 1,3-diethyl-2-methyl-4,5,6,7-tetrahydroindenyl group, a 1,2,3-triethyl-4,5,6,7-tetrahydroindenyl group, a 2-ethyl-4,5,6,7-tetrahydroindenyl group, a 1-methyl-2-ethyl-4,5,6,7-tetrahydroindenyl group, a 1,3-dimethyl-2-ethyl-4,5,6,7-tetrahydroindenyl group, a fluorenyl group, a 9-methylfluorenyl group, a 9-ethylfluorenyl group, a 1,2,3,4-tetrahydrofluorenyl group, a 9-methyl-1,2,3,4-tetrahydrofluorenyl group, a 9-ethyl-1,2,3,4-tetrahydrofluorenyl group, a 1,2,3,4,5,6,7,8-octahydrofluorenyl group, a 9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl group, a 9-ethyl-1,2,3,4,5,6,7,8-octahydrofluorenyl group, etc.
Specific examples of the transition metal compounds of formula (III) are mentioned below.
They are cyclopentadienyltitanium trichloride, cyclopentadienyltitaniumtrimethyl, cyclopenadienyltitanium trimethoxide, cyclopentadienyltitaniumtribenzyl, methylcyclopentadienyltitanium trichloride, methylcyclopentadienyltitaniumtrimethyl, methylcyclopentadienyltitanium trimethoxide, methylcyclopentadienyltitaniumtribenzyl, dimethylcyclopentadienyltitanium trichloride, dimethylcyclopentadienyltitaniumtrimethyl, dimethylcyclopentadienyltitanium trimethoxide, dimethylcyclopentadienyltitaniumtribenzyl, trimethylcyclopentadienyltitanium trichloride, trimethylcyclopentadienyltitaniumtrimethyl, trimethylcyclopentadienyltitanium trimethoxide, trimethylcyclopentadienyltitaniumtribenzyl, tetramethylcyclopentadienyltitanium trichloride, tetramethylcyclopentadienyltitaniumtrimethyl, tetramethylcyclopentadienyltitanium trimethoxide, tetramethylcyclopentadienyltitaniumtribenzyl, pentamethylcyclopentadienyltitanium trichioride, pentamethylcyclopentadienyltitaniumtrimethyl, pentamethylcyclopentadienyltitanium trimethoxide, pentamethylcyclopentadienyltitaniumtribenzyl, indenyltitanium trichloride, indenyltitanium trimethyl, indenyltitanium trimethoxide, indenyltitaniumtribenzyl, 1-methylindenyltitanium trichloride, 1-methylindenyltitaniumtrimethyl, 1-methylindenyltitanium trimethoxide, 1-mtethylindenyltitaniumtribenzyl, 2-methylindenyltitanium trichloride, 2-methylindenyltitaniumtrimethyl, 2-mrethylindenyltitanium trimethoxide, 1-methylindenyltitaniumtribenzyl, 1,2-dimethylindenyltitanium trichloride, 1,2-dimethylindenyltitaniumtrimethyl, 1,2-dimethylindenyltitanium trimethoxide, 1,2-dimethylindenyltitaniumtribenzyl, 1,3-dimethylindenyltitanium trichloride, 1,3-dimethylindenyltitaniumtrimethyl, 1,3-dimethylindenyltitanium trimethoxide, 1,3-dimethylindenyltitaniumtribenzyl, 1,2,3-trimethylindenyltitanium trichloride, 1,2,3-trimethylindenyltitaniumtrimethyl, 1,2,3-trimethylindenyltitanium trimethoxide, 1,2,3-trimethylindenyltitaniumtribenzyl, 1,2,3,4,5,6,7-heptamethylindenyltitanium trichloride, 1,2,3,4,5,6,7-heptamethylindenyltitaniumtrimethyl, 1,2,3,4,5,6,7-heptamethylindenyltitanium triethoxide, 1,2,3,4,5,6,7-heptamethylindenyltitaniumtribenzyl, 4,5,6,7-tetrahydroindenyltitaniumn trichloride, 4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 4,5,6,7-tetrahydroindenyltitanium trimethoxide, 4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1-methyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1-methyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1-methyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1-methyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 2-methyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 2-methyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 2-methyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1,2-dimethyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1,2-dimethyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1,2-dimethyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1,2-dimethyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1,3-dimethyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1,3-dimethyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1,3-dimethyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1,3-dimethyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1-ethyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1-ethyl-4,5,6,7-tetrahydroindenyltitaniuntrimethyl, 1-ethyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1-ethyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1-ethyl-2-methyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1-ethyl-2-methyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1-ethyl-2-methyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1-ethyl-2-methyl-4,5,6,7-tetrahydroindenyltitaniuntribenzyl, 1-ethyl-3-methyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1-ethyl-3-methyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1-ethyl-3-methyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1-ethyl-3-methyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1-ethyl-3-methyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1-ethyl-2,3-dimethyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1-ethyl-2,3-dimethyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1-ethyl-2,3-dimethyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1-ethyl-2,3-dimethyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1,2-diethyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1,2-diethyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1,2-diethyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1,2-diethyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1,2-diethyl-3-methyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1,2-diethyl-3-methyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1,2-diethyl-3-methyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1,2-diethyl-3-methyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1,3-diethyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1,3-diethyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1,3-diethyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1,3-diethyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1,3-diethyl-2-methyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1,3-diethyl-2-methyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1,3-diethyl-2-methyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1,3-diethyl-2-methyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1,2,3-triethyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1,2,3-triethyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1,2,3-triethyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1,2,3-triethyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 2-ethyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 2-ethyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 2-ethyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 2-ethyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1-methyl-2-ethyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1-methyl-2-ethyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1-methyl-2-ethyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1-methyl-2-ethyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1,3-dimethyl-2-ethyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1,3-dimethyl-2-ethyl-4,5,6,7-tetrahydroindenyltitaniumtrimethyl, 1,3-dimethyl-2-ethyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide, 1,3-dimethyl-2-ethyl-4,5,6,7-tetrahydroindenyltitaniumtribenzyl, 1,2,3,4-tetrahydrofluorenyltitanium trichloride, 1,2,3,4-tetrahydrofluorenyltitaniumtrimethyl, 1,2,3,4-tetrahydrofluorenyltitanium trimethoxide, 1,2,3,4-tetrahydrofluorenyltitaniumtribenzyl, 9-methyl-1,2,3,4-tetrahydrofluorenyltitanium trichloride, 9-methyl-1,2,3,4-tetrahydrofluorenyltitaniumtrimethyl, 9-methyl-1,2,3,4-tetrahydrofluorenyltitanium trimethoxide, 9-methyl-1,2,3,4-tetrahydrofluorenyltitaniumtribenzyl, 9-ethyl-1,2,3,4-tetrahydrofluorenyltitanium trichloride, 9-ethyl-1,2,3,4-tetrahydrofluorenyltitaniumtrimethyl, 9-ethyl-1,2,3,4-tetrahydrofluorenyltitanium trimethoxide, 9-ethyl-1,2,3,4-tetrahydrofluorenyltitaniumtribenzyl, 1,2,3,4,5,6,7,8-octahydrofluorenyltitanium trichloride, 1,2,3,4,5,6,7,8-octahydrofluorenyltitaniumtrimethyl, 1,2,3,4,5,6,7,8-octahydrofluorenyltitanium trimethoxide, 1,2,3,4,5,6,7,8-octahydrofluorenyltitaniumtribenzyl, 9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyltitanium trichloride, 9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyltitaniumtrimethyl, 9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyltitanium trimethoxide, 9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyltitanium trichloride, 9-ethyl-1,2,3,4,5,6,7,8-octahydrofluorenyltitaniumtrimethyl, 9-ethyl-1,2,3,4,5,6,7,8-octahydrofluorenyltitanium trimethoxide, 9-ethyl-1, 2,3,4,5,6,7,8-octahydrofluorenyltitaniumtribenzyl, etc.; as well as their derivatives to be produced by substituting the titanium element in those compounds with zirconium or hafnium, or with any other element of different Groups, and also their analogues having a transition metal element of lanthanides. However, these are not limitative. Of these, preferred are titanium compounds.
The catalyst of the invention may contain one or more of the transition metal compounds either singly or as combined for the component (A).
(B) Organoaluminiumoxy Compound:
The organoaluminiumoxy compound for the component (B) is not specifically defined, and may be any one that may be obtained through reaction of an organoaluminium compound with water. As specific examples of the compound, mentioned are commercial products from Albemarle Corporation and Shering Corporation, etc.
Also mentioned are aluminiumoxy compounds of so-called linear aluminoxanes of the following general formula (XI) and cyclic aluminoxanes of the following general formula (XII), of which the basic structures are disclosed in many known references. 
wherein R9 represents a hydrocarbon group, such as an alkyl, alkenyl, aryl, arylalkyl or the like group having from 1 to 20, preferably from 1 to 12 carbon atoms, or a halogen atom; w indicates a degree of mean polymerization, and is an integer generally falling between 2 and 50, preferably between 2 and 40; and plural R9""s may be the same or different. 
wherein R9 and w have the same meanings as in formula (XI).
For producing the aluminoxanes, an organoaluminium compound may be contacted with a condensation agent such as water or the like, for which the mode of condensation is not specifically defined and the reactants may be reacted in any ordinary manner. For it, for example, employable is (1) a method comprising dissolving an organoaluminium compound in an organic solvent followed by contacting it with water; (2) a method comprising directly adding an organoaluminium compound to the polymerization system that requires the intended aluminoxane, followed by adding water thereto; (3) a method comprising reacting an organoaluminium compound with crystal water existing in metal salts and the like or with water having adsorbed by inorganic or organic substances; or (4) a method comprising reacting a tetraalkyldialuminoxane with a trialkylaluminium and then with water. The aluminoxanes may be insoluble in toluene.
Any others produced according to the techniques disclosed in known references are also usable herein. The references are, for example, Japanese Patent Laid-Open Nos. 328520/1997, 278824/1997, etc. In the invention, one or more of the aluminiumoxy compounds mentioned above may be used either singly or as combined.
The starting organoaluminium compounds for the organoaluminiumoxy compounds for use in the invention are not specifically defined, and include various types of organoaluminium compounds. For example, usable are alkyl-having aluminium compounds of the following general formula (XIII):
R10mAl(OR11)nX3-m-nxe2x80x83xe2x80x83(XIII)
wherein R10 and R11 each represent an alkyl group having from 1 to 8, preferably from 1 to 4 carbon atoms; X represents a hydrogen atom or a halogen atom; 0 less than mxe2x89xa63, preferably m=2 or 3, most preferably m=3; 0xe2x89xa6n less than 3, preferably n=0 or 1.
Examples of the compounds are trialkylaluminium compounds such as trimethylaluminium, triethylaluminium, tripropylaluminium, triisopropylaluminium, tri-n-butylmethylaluminium, triisobutylaluminium, tri-sec-butylmethylaluminium, tri-tert-butylmethylaluminium, tripentylaluminium, trihexylaluminium, trioctylaluminium, tridecylaluminium, tricyclohexylaluminium, tricyclooctylaluminium, etc.; halogen-, alkoxy- or hydroxyl-having alkylaluminium compounds such as dimethylaluminium chloride, diethylaluminium chloride, ethylaluminium sesquichloride, dimethylaluminium methoxide, diethylaluminium methoxide, dimethylaluminium hydroxide, diethylaluminium hydroxide, etc.; hydrogen-having alkylaluminium compounds such as dimethylaluminium hydride, diisobutylaluminium hydride, etc. In the invention, one or more of the organic aluminium compounds mentioned above may be used either singly or as combined.
For the component (B), preferred are organoaluminiumoxy compounds which are obtained through reaction of an organoaluminium compound with water and which are soluble in hydrocarbon solvents. The merits of the organoaluminiumoxy compounds soluble in hydrocarbon solvents are that, when they are used as a catalyst for olefin polymerization, the polymers obtained could have good morphology as containing a reduced amount of fine powder and having a large mean particle size, and, in addition, the organoaluminiumoxy compounds not carried on inorganic compounds could be recycled. The hydrocarbon solvents include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, etc.; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, etc.; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, etc.; petroleum fractions such as naphtha, kerosene, light gas oil, etc. Of those, especially preferred are aromatic hydrocarbons. Also preferably, the organoaluminiumoxy compound for use in the invention contains at most 10% by weight of an organoaluminium compound remaining therein, when measured through 1H-NMR, since the proportion of the organoaluminiumoxy compound capable of being carried on an inorganic compound (this is hereinafter referred to as an on-carrier percentage of the compound) increases. More preferably, the amount of the organoaluminium compound remaining in the organoaluminiumoxy compound falls between 3 and 5% by weight or lower, most preferably between 2 and 4% by weight or lower. If the amount of the organoaluminium compound remaining in the organoaluminiumoxy compound is larger than 10% by weight, it is undesirable since the on-carrier percentage of the organoaluminiumoxy compound will decrease and the polymerization activity thereof will thereby decrease.
The fraction not soluble in hydrocarbon solvents such as those mentioned above may be removed from the organoaluminiumoxy compound, for which the method is not specifically defined. For example, one method comprises processing the organoaluminiumoxy compound in a hydrocarbon solvent to lead to spontaneous precipitation of the fraction not soluble in the solvent, followed by removing the insoluble fraction through decantation. Another method comprises removing the insoluble fraction through centrifugation or the like. More preferably, the thus-recovered, soluble fraction is filtered through a G5 glass filter or the like in a nitrogen atmosphere, whereby the insoluble fraction is more completely removed from it. The thus-processed organoaluminiumoxy compound will have an increased amount of a gelled fraction with the lapse of time. Therefore, it is desirable that the organoaluminiumoxy compound is used within 48 hours after its preparation, more preferably immediately after its preparation. The ratio of the organoaluminiumoxy compound to the hydrocarbon solvent is not specifically defined, but it is desirable that the amount of the organoaluminiumoxy compound falls between 0.5 and 10 mols in terms of the aluminium atom in the compound relative to 1 liter of the hydrocarbon solvent.
For obtaining the organoaluminiumoxy compound in which the amount of the organoaluminium compound remaining is at most 10% by weight, the method is not specifically defined. For example, one method comprises drying up the solution of the organoaluminiumoxy compound to completely remove the solvent from it through distillation to dryness under heat under reduced pressure (this is referred to as a drying-up method). In the drying-up method under heat under reduced pressure, it is desirable that the solvent is evaporated away at a temperature not higher than 80xc2x0 C., more preferably not higher than 60xc2x0 C. At temperatures of 80xc2x0 C. or higher, the insoluble fraction in the solution of the organoaluminiumoxy compound will greatly increase, and the activity of the transition metal-carried catalyst that contains the compound will be low. The degree of the reduced pressure in the process may be generally 30 mmHg or lower, but preferably 20 mmHg or lower. Determination of organoaluminiums may be effected in accordance with the disclosure in Organometallics, Vol. 17, No. 10, (1998), pp. 1941-1945.
(C) Carrier:
The carrier for use in the invention is not specifically defined, and may be any of inorganic oxide carriers, and other inorganic carriers and organic carriers. From the viewpoint of polymer morphology control, preferred are inorganic oxide carriers and other inorganic carriers. As examples of the inorganic oxide carriers and other inorganic carriers, mentioned are inorganic compounds that contain at least one element selected from Groups 2 to 4 and Groups 12 to 14 of the Periodic Table. At least one element selected from Groups 2 to 4 and Groups 12 to 14 of the Periodic Table is C, Mg, Al, Si, Ca, Sc, Ti, B, Tl, Ge, Sn, Zn, Ba, Pb, Y, Sr, Th, etc. As the carrier for use in the invention, preferred are inorganic compounds especially inorganic oxides, as their capability to carry the catalyst components thereon is good. The inorganic oxides include SiO2, Al2O3, MgO, ZrO2, TiO2, Fe2O3, B2O3, CaO, ZnO, BaO, ThO2, etc. In addition, also employable are silica-alumina, zeolite, ferrite, glass fibers, etc. Zeolite includes natural substances such as mordenite, etc.; synthetic products such as zeolite X, zeolite Y, zeolite A, etc.; high-silica zeolite with (SiO2/Al2O3)xe2x89xa7 20, such as typically ZSM-5; zeolite analogues such as ALPO, SAPO, etc.; amorphous zeolite such as MCM-41, MCM-50, etc., any of which is employable herein.
The inorganic oxides may contain minor carbonates, nitrates, sulfates, etc. Apart from the inorganic compounds noted above, also employable herein are magnesium compounds of a general formula MgR12xX2y and their complexes. In the formula, R12 represents an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, or an aryl group having from 6 to 20 carbon atoms; X2 represents a halogen atom, or an alkyl group having from 1 to 20 carbon atoms; x falls between 0 and 2, y falls between 0 and 2, and x+y=2. Plural R12""s and plural X2""s may be the same or different. Specific examples of the compounds are MgCl2, Mg(OC2H5)2, etc. The organic carriers usable herein include polymers such as polystyrenes, styrene-divinylbenzene copolymers, polyethylenes, polypropylenes, substituted polystyrenes, polyarylates, etc.; as well as starch, carbon, etc.
Preferably, the carrier for use in the invention is porous. The porous carrier shall have a pore volume of generally from 0.1 to 5 cm3/g, but preferably from 0.3 to 3 cm3/g, and a specific surface area of generally from 1 to 1000 m2/g, but preferably from 50 to 500 m2/g. If any of its specific surface area and pore volume oversteps the defined range, the catalyst activity will below. The pore volume and the specific surface area of the carrier may be derived from the volume of the nitrogen gas having been absorbed by the carrier, for example, according to the BET method (see J. Am. Chem. Soc., Vol. 60, p. 309 (1983)).
More preferably, the carrier for use in the invention is in the form of fine particles, as its capability to carry catalyst components thereon is better. Though varying depending on its type and on the method for producing it, the particulate carrier may have a mean particle size generally falling between 1 and 300 xcexcm, but preferably between 10 and 200 xcexcm, more preferably between 20 and 100 xcexcm. If the particle size of the carrier is too small, fine powder will increase in the polymers produced; but if too large, coarse and large grains will increase in the polymers produced to thereby lower the bulk density of the polymers, and, in addition, the carrier will clog hoppers. It is desirable that the carrier is baked generally at a temperature falling between 120 and 1000xc2x0 C., but preferably between 200 and 800xc2x0 C., before used in the invention.
As the carrier for use in the invention, preferred are MgCl2, MgCl(OC2H5), Mg(OC2H5)2, SiO2, Al2O3, etc. Of these, more preferred are SiO2 and Al2O3.
The method for producing the olefin polymerization catalyst of the invention is mentioned below. For producing the catalyst, two or more components of (A), (B) and (C) mentioned above are contacted with each other, and the condition for contacting them is not specifically defined. Like known Ziegler-Natta catalysts and metallocene catalysts, the catalyst of the invention may be produced under ordinary conditions. For example, the components may be contacted with each other in an inert gas atmosphere optionally containing a solvent, at a temperature falling between xe2x88x9230xc2x0 C. and the boiling point of the solvent used. The inert gas may be argon gas or nitrogen gas. The solvent includes aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, etc.; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, etc.; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, etc.; petroleum fractions such as naphtha, kerosene, light gas oil, etc. Of those, especially preferred are aromatic hydrocarbons.
The order of contacting them is not specifically defined. For example, any two of the components (A), (B) and (C) may be contacted at a time, or any one of them may be contacted with the other one. The three components may be contacted all at a time, or any two of them may be first contacted with each other and then with the remaining one. While being contacted with each other, the components are exposed to elastic waves at least once during the process of contacting them. For example, any of the following methods are employable for contacting the three components with each other.
(1) A method of contacting the three components (A), (B) and (C) all at a time while being exposed to elastic waves;
(2) A method of contacting (A) with (B) while being exposed to elastic waves, and then further contacting them with (C);
(3) A method of contacting (A) with (B) while being exposed to elastic waves, and then further contacting them with (C) while still being exposed to elastic waves;
(4) A method of contacting (A) with (B), followed by further contacting them with (C) while being exposed to elastic waves;
(5) A method of contacting (A) with (C) while being exposed to elastic waves, and then further contacting them with (B);
(6) A method of contacting (A) with (C) while being exposed to elastic waves, and then further contacting them with (B) while still being exposed to elastic waves;
(7) A method of contacting (A) with (C), followed by further contacting them with (B) while being exposed to elastic waves;
(8) A method of contacting (B) with (C) while being exposed to elastic waves, and then further contacting them with (A);
(9) A method of contacting (B) with (C) while being exposed to elastic waves, and then further contacting them with (A) while still being exposed to elastic waves;
(10) A method of contacting (B) with (C), followed by further contacting them with (A) while being exposed to elastic waves.
Of these methods, preferred are (9) and (10).
Elastic waves to which the catalyst components are exposed in the invention are of elastic vibration that propagates through elastic materials. In general, they are longitudinal waves which contract and expand in the direction of their travel, but are often transverse waves around reactor walls and around the interface at which the catalyst components are contacted with each other. In the invention, any known elastic waves are employable with no specific limitation. In general, preferred are sound waves, and especially preferred are ultrasonic waves. Concretely, the elastic waves for use in the invention are preferably ultrasonic waves of which the frequency falls between 1 and 1000 kHz, more preferably between 10 and 500 kHz, even more preferably between 20 and 300 kHz. The power of the ultrasonic waves is preferably at least 10 W, more preferably at least 100W, even more preferably at least 500 W. It is desirable that the catalyst components are exposed to the elastic waves of that type in such a manner that the wave strength could be at least 0.01 W/cm2, more preferably at least 0.05 W/cm2, even more preferably from 0.07 to 100 W/cm2, at the inner wall of the reactor where the catalyst components are contacted with each other. The strength of ultrasonic waves can be obtained as follows. A reactor is filled with a reference liquid, water, to which are applied ultrasonic waves. In that condition, the sound pressure in the reactor is measured with a sound pressure meter (Kaijol""s TYPE 1501, provided with a probe of UTSP-60 and a cable of USC-150), from which is obtained the ultrasonic wave strength according to the following formula:
I=P2/xcfx81c
wherein I indicates the ultrasonic wave strength; P indicates the sound pressure; xcfx81 indicates the density of the medium (water); and c indicates the sound wave velocity in the medium.
In the invention, elastic waves may be applied to the reactor in which the catalyst components are contacted with each other, from the wave-generating surface disposed outside the reactor; or the wave-generating surface may be disposed inside the reactor so that the reaction system in the reactor could be directly exposed to elastic waves from it. When passing through the reactor wall, elastic waves are often attenuated owing to transmission loss (the ratio of the transmitted wave energy to the incident wave energy at the point of measurement) Therefore, in the invention, the wave-generating surface is preferably disposed inside the reactor so that the catalyst components being contacted with each other therein could be directly exposed to elastic waves from it. Elastic waves are attenuated more in the place remoter from the wave source. Therefore, it is desirable to appropriately determine and control the position of the wave-generating surface, the shape of the reactor, the wave strength at the wave-generating surface, the disposition and the number of the wave sources and other conditions for wave exposure. Elastic waves have the capability to agitate the reaction system. Therefore, irrespective of its shape, the reactor for use herein does not always require a stirrer, but is preferably equipped with a stirrer. The temperature at which the reaction system is exposed to ultrasonic waves may fall between xe2x88x92200xc2x0 C. and the boiling point of the solvent used, but preferably between room temperature and 100xc2x0 C. The exposure time is not specifically defined so far as the intended catalyst components could be obtained within it, but is generally within 20 hours, preferably within 10 hours.
The blend ratio of the components (A), (B) and (C) that are contacted with each other to form the olefin polymerization catalyst of the invention may be generally such that the amount of the component (B) falls between 0.0001 and 200000 mols, preferably between 30 and 5000 mols, relative to one mol of the component (A), and the amount of the component (C) falls between 0.001 and 10 g, preferably between 0.01 and 1 g, relative to one mol of the component (A). If the blend ratio oversteps the defined ranges, the activity of the catalyst will be low.
As having been exposed to elastic waves in the manner mentioned above, the contact efficiency of the components of the olefin polymerization catalyst of the invention is improved, and the polymerization activity of the catalyst is thereby increased. For example, when the catalyst contains the component (C) serving as a carrier, the catalyst components can be well carried on the carrier to its depth, since they are exposed to elastic waves, being different from those carried on the carrier in an ordinary manner. As a result, the number of the active points effective for olefin polymerization in the catalyst increases, and the activity of the catalyst is thereby enhanced. The olefin polymerization catalyst of the invention does not always require the component (C). In this case, the catalyst components are in a uniform system, and the uniform-system catalyst of the invention also enjoys the same effect as above. Preferably, however, the catalyst contains the component (C), and is in the form of a non-uniform system.
For producing the olefin polymerization catalyst of the invention, the components (A), (B) and optionally (C) are contacted with each other. In the method, the components are exposed to elastic waves at least in any step of contacting them with each other. The details of the method for producing the olefin polymerization catalyst are described hereinabove.
The method of the invention for producing olefinic polymers includes homopolymerization of olefins or copolymerization of olefins with other olefins and/or other monomers (that is, copolymerization of different types of olefins, or copolymerization of olefins with other monomers, or copolymerization of different types of olefins with other monomers) in the presence of the olefin polymerization catalyst optionally along with an organoaluminium compound.
As the organoaluminium compound, usable are the compounds of formulae (XI) to (XIII) mentioned above. Preferred are trialkylaluminium compounds such as triisobutylaluminium, etc. The amount of the organoaluminium compound to be used may be generally such that the molar ratio of aluminium in the organoaluminium compound to the transition metal in the component (A) falls between 1:0 and 1:10000.
Olefins to be polymerized in the invention are not specifically defined, but preferred are xcex1-olefins having from 2 to 20 carbon atoms. More preferred are ethylene, propylene and styrene; and even more preferred is propylene. Polypropylenes obtained by polymerizing propylene in the presence of the olefin polymerization catalyst of the invention could have a high degree of stereospecificity and a high molecular weight.
Olefins to be polymerized herein include, for example, xcex1-olefins such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 4-phenyl-1-butene, 1-pentene, 3-methyl-l-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 6-phenyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, etc.; halogen-substituted xcex1-olefins such as hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene, 3,4-dichloro-1-butene, etc.; and cyclic olefins such as cyclopentene, cyclohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 5-benzylnorbornene, etc.; Styrenic monomers to be polymerized herein include, for example, styrene; alkylstyrenes such as p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene, m-butylstyrene, mesitylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, etc.; alkoxystyrenes such as p-methoxystyrene, o-methoxystyrene, m-methoxystyrene, etc.; halogenostyrenes such as p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene, etc.; and also trimethylsilylstyrene, vinylbenzoates, divinylbenzene.
In the invention, one or more olefins may be homopolymerized or copolymerized either singly or as combined. Where two or more different olefins are copolymerized, the olefins noted above may be combined in any desired manner.
In the invention, olefins such as those mentioned above may be copolymerized with any other comonomers. The comonomers include, for example, linear diolefins such as butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, etc.; polycyclic olefins such as norbornene, 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-norbornene, etc.; cyclic diolefins such as norbornadiene, 5-ethylidenenorbornene, 5-vinylnorbornene, dicyclopentadiene, etc.; and unsaturated esters such as ethyl acrylate, methyl methacrylate, etc.
The mode of olefin polymerization is not specifically defined, and herein employable is any desired polymerization mode of slurry polymerization, solution polymerization, vapor-phase polymerization, bulk polymerization or suspension polymerization. Preferred are modes of slurry polymerization and vapor-phase polymerization. Solvents may be used in polymerization of the monomers. They include hydrocarbons and halogenohydrocarbons such as benzene, toluene, xylene, n-hexane, n-heptane, cyclohexane, chloromethylene, chloroform, 1,2-dichloroethane, chlorobenzene, etc. One or more such solvents may be used either singly or as combined. Depending on their type, the monomers to be polymerized may also serve as solvents.
In view of the catalytic activity for polymerization and of the reactor efficiency, it is desirable that the amount of the catalyst to be in the polymerization system is so controlled that the amount of the component (A) could fall generally between 0.1 and 100 xcexcmols, but preferably between 0.5 and 25 xcexcmols, in one liter of the solvent in the system.
Regarding the polymerization condition, the pressure may fall generally between ordinary pressure and 200 MPaxc2x7G. The reaction temperature may fall generally between xe2x88x9250 and 250xc2x0 C. For controlling the molecular weight of the polymers to be produced, the type and the amount of the catalytic components to be used and the polymerization temperature will be suitably selected. If desired, hydrogen may be introduced into the polymerization system for that purpose.